JPH0768542B2 - Liquid bleaching composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid detergent composition comprising an aqueous substrate, a detergent active material and a bleaching material.

EP 293040 (P & G) proposes to formulate a liquid solvent composition consisting of a perborate bleaching material and a water-soluble solvent system in order to improve the stability of the bleaching agent in the aqueous phase. Similar solvents in combination with bleach are also proposed in EP 294904 (P & G).

When formulating a liquid aqueous detergent composition consisting of a bleaching material,
It has been found that bleach instability problems often arise. Although not fully understood yet, it is believed that this instability results from the solubilization of the bleaching material in the aqueous phase, followed by the decomposition of the dissolved bleaching material.

It has now been found, surprisingly, that it is possible to formulate stable bleach-containing liquid aqueous detergent compositions, if said composition also comprises certain silicate-stabilizing materials.

The present invention therefore relates to an aqueous base material containing 10 to 30% by weight of a detergent active material, 1 to 40% by weight of solid particulate peroxygen bleaching material and 0.4 to 5% by weight of an alkali metal silicate material, preferably two. It relates to a liquid detergent composition comprising a silicate material.

Bleaching Material The composition according to the invention consists of a bleaching material, which is preferably a peroxygen bleaching agent. The bleaching component may be present in the system in dissolved form, but it is preferred to solubilize only one part of the peroxygen bleaching agent, the balance being preferably present as solid peroxygen particles suspended in the system.

Examples of suitable bleaching compounds include perborates, persulfates, peroxydisulfates, perphosphates, and crystalline peroxyhydrates formed by reacting hydrogen peroxide with urea or alkali metal carbonates. . In addition, encapsulated bleach can be used. Suitable bleaches are only partially soluble in the system. The use of perborate or percarbonate bleach is particularly preferred.

The bleaching component is preferably 0.1 to 15% by weight active oxygen, more preferably 0.5 to 10% active oxygen, typically 1.0 to 5.
It is added in an amount corresponding to 0% active oxygen. Typical amounts of bleaching agents are from 1 to 40% by weight, based on the aqueous composition, more preferably from 7 to 30% and particularly preferably from 10 to 25% by weight.

Silicate Material The composition of the present invention further comprises an alkali metal silicate material.

Suitable silicate materials are, for example, sodium and potassium silicates, such as sodium metasilicate and sodium disilicate. The use of alkali metal disilicates is preferred.

Although not fully understood yet, it is believed that the alkali metal silicate material may serve two functions, firstly it prevents solubilization of the bleaching material and reduces the amount of labile dissolved bleaching agent. Minimize, and secondly, it prevents decomposition of the dissolved bleaching material.

The level of alkali metal silicate material is preferably 0.4-
5%.

Detergent Active Material The composition of the present invention further comprises a detergent active material. Surprisingly, it has been found that the combination of bleaching material and alkali metal silicate material is suitable for use in ready-to-use aqueous liquid detergent compositions.

In its broadest sense, a detergent active material can generally consist of one or more surface-active agents, including anionic, cationic, nonionic, zwitterionic and zwitterionic types, and (If compatible with each other)
It can be selected from the mixture. For example, this can be found in the literature [“Surface Active Agents” vol.I, by Schwatrz
& Perry, Interscience 1949 and “Surface Active
Agents "vol.II, Schwartz, Perry & Berch (Interscienc
e 1958), current edition of “McCutcheon ′s Emulsif
iers & Deterqents ", Publisher McCutcheon division of
Manufacturing Confectioners Company or Tensid−
Taschenburch ", H, Stache, 2nd End., Carl Hanser Verla
g, Munchen & Wien, 1981].

Suitable nonionic surfactants are especially the reaction products of compounds having hydrophobic groups and reactive hydrogen atoms, such as aliphatic alcohols, acids, amides or alkylphenols and alkylene oxides, especially ethylene oxide (alone or with propylene oxide). ). Certain nonionic detergent compounds include alkyl (C ₆ -C ₁₈ ) primary or secondary linear or branched chain alcohols with ethylene oxide, and ethylene oxide condensed with the reaction product of propylene oxide and ethylenediamine. It is a created product. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.

Furthermore, the use of salting-out-resistant active substances, for example as described in EP 328177, in particular EP 70074.
It is also possible to use alkyl polyglycoside surfactants as disclosed in US Pat.

Suitable anionic surfactants are generally water-soluble alkali metal salts of organic sulphates and sulphonates with alkyl groups having from about 8 to about 22 carbon atoms, the term alkyl being the alkyl part of the higher acyl groups. Is used inclusively. Examples of synthetic anionic detergent compounds suitable are those obtained sodium and potassium alkyl sulfates, especially the higher (C ₈ ~C ₁₈₎ alcohols produced for example from tallow oil or coconut oil and sulfated alkyl (C ₉ ~ C ₂₀₎ sodium benzenesulfonate and potassium, particularly linear secondary alkyl (C ₁₀ ~C ₁₅₎ sodium benzenesulfonate, alkyl glyceryl ether sodium sulfate, higher alcohol and petroleum are particularly derived from tallow oil or coconut oil Derived synthetic alcohol ethers; coconut oil fats monoglycerdosulfate and sodium sulfonate; higher (C ₈ ~
C ₁₈ ) Sodium and potassium salts of sulfuric acid esters of fatty alcohol-alkylene oxide (especially ethylene oxide) reaction products; reaction of fatty acids such as coconut fatty acid esterified with isethionic acid and neutralized with sodium hydroxide Products; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulfonates, such as those obtained by reacting α-olefins (C ₈ -C ₂₀ ) with sodium bisulfite, and paraffins with SO ₂ and Cl ₂ . Derived by reacting and then hydrolyzing with a base to form a random sulfonate; and olefin sulfonates (this term is olefin,
In particular C ₁₀ -C ₂₀ alpha-olefin is reacted with SO _3, then it is hydrolyzed is used in order to explain the created material) as well as neutralizing the reaction product. Suitable anionic detergent compounds are (C ₁₁ ~C ₁₅₎ sodium alkylbenzene sulfonate and first (C ₁₀ ~C ₁₈₎ alkyl sodium or potassium sulphate.

In addition, alkali metal soaps of fatty acids, especially acids with 12 to 18 carbon atoms (eg fatty acids derived from oleic acid, ricinoleic acid and castor oil, alkylsuccinic acids), rapeseed oil, groundnut oil, coconut oil, coconut kernels. It may also include soaps of oils or mixtures thereof, which is often preferred. Sodium or potassium soaps of these acids can be used.

The total detergent active material may be present at 10-30% by weight of the total composition. However, one suitable class of compositions comprises at least 20%, particularly preferably at least 25% and in particular at least 30% of detergent active material, by weight of the total composition.

Optional Ingredients The compositions of the present invention can be unstructured (isotropic) or structured. The structured liquids of the present invention can be internally structured, in which case they can be structured by the detergent active material in the composition or can be externally structured, in this case with an external structure-forming agent. Give structure. Preferably the compositions of the present invention are internally structured.

Some of the different types of possible active structured materials are described in the literature [HA Barnes, "Detergents", Ch.2., K. Walters (Ed),
“Rheometry: Industrial Applications”, J.Wiley & So
ns, Letchworth 1980]. Generally, the degree of alignment of this type of system increases with increasing concentrations of surfactant and / or electrolyte. At very low concentrations the surfactant can be present as a molecular solution or as a solution of spherical micelles, both of which are isotropic. By adding other surfactants and / or electrolytes, a structured (anisotropic) system can be produced. These are respectively referred to in various terms such as rod-micelles, planar lamellar structures, lamellar droplets and liquid crystal phases. Often, different researchers use different terms to describe structures that are actually the same. For example, in EP-A-151884 the lamellar droplets are called "spherulite". The presence and identification of surfactant structured systems in liquids can be determined by means known to those skilled in the art, such as optical techniques, various rheological measurements, X-ray or neutron diffraction and often electron microscopy. .

If the composition is a lamellar droplet structure, it is often preferred that the aqueous continuous phase contain dissolved electrolyte. As used herein, the term electrolyte means any ionic water-soluble substance. However, in a lamellar dispersion, not all electrolytes are necessarily dissolved, and they may be suspended as solid particles. This is because the total electrolyte concentration of the liquid is higher than the solubility limit field of this electrolyte. Mixtures of electrolytes may also be used, one or more of the electrolytes being present in the dissolved aqueous phase while one or more being present substantially only in the suspended solid phase. Two or more electrolytes can also be distributed between these two phases in a roughly proportional manner. In part, this depends on the processing method (eg, the order of addition of each component). The term "salt", on the other hand, encompasses all organic and inorganic substances that may be included, other than surfactants and water, which may or may not be in the ionic form, and the term may be used as a secondary electrolyte (water soluble Substance).

Selection of the type of surfactant and its ratio to obtain a stable liquid with the required structure is well within the knowledge of one of ordinary skill in the art. However, an important subclass of useful compositions can be said to be those in which the detergent active material consists of a blend of different surfactants. Typical formulations useful in laundry laundry compositions include those where the predominant surfactant consists of nonionic and / or nonalkoxylated anionic and / or alkoxylated anionic surfactants.

In the case of surfactant formulations, the exact proportions of the components which lead to this kind of stability and viscosity depend on the type and amount of electrolyte, as in the case of conventional structured liquids.

However, preferably the composition is 1-60%, especially 10-45%.
% Salting out electrolyte. Salting out electrolyte is EP-A-
It has the meaning described in 79646, ie the salting out electrolyte has a lyotropic number of less than 9.5. If necessary, some salt-soluble electrolyte (specified in the above patent specification)
May also be included, provided that they are of a type and amount compatible with the other ingredients, and the composition is still within the scope of the invention as described herein. Some or all of the electrolytes (either salt soluble or salting out) or substantially water insoluble salts that may be present may have detergent builder properties. In any case, it is preferred that the composition according to the invention comprises a detergent builder material, some or all of which may be the electrolyte.
The builder material is any that can reduce the level of free calcium ions in the wash liquor, preferably other such as the development of alkaline pH, suspension of soil removed from the fabric and dispersion of the fabric softening clay material. To the composition. Preferably, the salting out electrolyte is composed of citrate.

Examples of phosphorus-containing inorganic detergent builders, when present, include water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include the sodium and potassium salts of tripolyphosphoric acid, phosphoric acid and hexametaphosphoric acid. A phosphonate sequestration builder can also be used.

Examples of phosphorus-free inorganic detergent builders, when present, include water soluble alkali metal carbonates, bicarbonates, silicates, and crystalline and amorphous aluminosilicates.
Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonate, and zeolites.

In the range of inorganic builders, the use of potassium salts is preferred, which preferably comprises electrolytes which increase the solubility of other electrolytes, for example the solubility of the sodium salt. This allows the amount of dissolved electrolyte to be controlled by the British patent GB 13
It can be significantly increased (crystal dissolution) as described in 02543.

Examples of organic detergent builders, when present, include alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetylcarboxylates and polyhydroxysulfonates. Specific examples include ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, CMOS, TMS, TDS, melodiic acid benzene polycarboxylic acid and sodium, potassium, lithium, ammonium and substituted ammonium salts of citric acid.

Preferably, the level of non-soap builder material is 0 to 50% by weight of the composition, more preferably 5 to 40% and particularly preferably 10 to 35%.

In the range of organic builders, it is also desirable to incorporate polymers which are only partially soluble in the aqueous continuous phase, as described in EP 301,882. This allows viscosity reduction (based on soluble polymer) as well as incorporation in high enough amounts to achieve secondary benefits (especially building). Because the part that does not dissolve is
This is because there is no instability that would occur if almost all were dissolved. Typical amounts are 0.5-4.5% by weight.

Further, the composition of the present invention may further contain another polymer in place of or in addition to the partially dissolved polymer, which other polymer is almost completely soluble in the aqueous phase. And the electrolyte resistance of sodium nitrilotriacetate of 5 g or more per 100 ml of a 5% by weight aqueous solution of the polymer, and the second polymer is 2% by weight of polyethylene glycol having an average molecular weight of 6000 in a 20% aqueous solution. % Or more of the vapor pressure of the aqueous solution, or lower, and the second polymer has a molecular weight of at least 1000. The use of polymers of this type is generally
It is described in EP 301,883. Typical level is 0.5 ~
It is 4.5% by weight.

The viscosity of the composition according to the invention is preferably 1,500 at 21 s ^-1 .
less than mPa · s, more preferably less than 1,000 mPa · s, especially 3
It is in the range of 0 to 900 mPa · s.

One way to control the viscosity and stability of the composition according to the invention is to include a viscosity-regulating polymeric material.

Suitable viscosity and / or stability modifying polymers for incorporation into the compositions of the present invention include peptizing polymers having a hydrophilic backbone and at least one hydrophobic side chain. Polymers of this kind are described, for example, in the applicant's co-pending European patent application EP 89201530.6 (EP 346995).

The deflocculating polymer for use in the detergent composition of the present invention can be anionic, nonionic or cationic. Anionic peptizable polymers are preferred.

The hydrophilic backbone of the polymer is typically a homopolymer, copolymer or terpolymer (more preferably its salt form) having carboxylic acid groups, such as maleic acid or acrylic acid polymers or copolymers thereof or vinyl ether, styrene etc. Is a copolymer with the monomer unit of. The hydrophobic chain is typically selected from saturated and unsaturated alkyl chains having, for example, 5 to 24 carbon atoms, optionally containing an alkoxylene or polyalkoxylene bond, such as 1 to 50 alkoxylene groups. It is attached to the backbone via a polyethoxy, polypropoxy or butyloxy (or a mixture thereof) bond. For example, in some configurations the side chains have the properties of substantially nonionic surfactants. Suitable anionic polymers are the applicant's co-pending European patent applications
It is disclosed in EP 89201530.6 (EP 346995).

Preferably, the amount of viscosity modifying polymer is 0,0 based on the total composition.
It is 1 to 5% by weight, and more preferably 0.2 to 2%.

The composition of the present invention may further include substances for adjusting pH. It is preferable to use a weak acid to lower the pH, particularly preferably an organic acid, and C _1-8
The use of carboxylic acid is more preferred, and the use of citric acid is most preferred. The use of these pH-lowering agents is particularly suitable when the composition according to the invention contains enzymes such as amylases, proteases and lipolases.

In addition to the components listed above, the presence of numerous optional components
E.g. alkanolamides, especially palm kernel fat
Acid derived from coconut and coconut fatty acids
Foaming promoters such as amides such as clays, amines and
And fabric softeners such as amine oxides, foam control agents, and
Inorganic salts such as sodium sulphate, as well as very small amounts
Generally present in, fluorescent agents, fragrances, germicides, colorants,
And for example proteases, cellulases, amylases
And lipase (including Lipolaza (registered trademark), Novo Inc.
An enzyme such as “include” can also be included. Protea
Suitable examples of enzyme (Novo), Makisaka
The (Gist-Brocade), Opticlean (MK
Company C) or AP122 (Showa Denko), Alcalase , Ma
Xatase , Esperase , Optimase ,Professional
The proteinase K and subtilisin BPN. Suitable
Polase is for example Lipolase (Novo), Amanori
Pase , Mate-lipase, lipoteam , SP225, S
P285, Toyo Jozo Lipase. Suitable
Midase is, for example, Termamyl (Novo registered company
Standard) and maxamil Is. A suitable cellulase is
Le Team (Novo).

The composition according to the invention preferably comprises 10 to 80% by weight of water, more preferably 15 to 60% and especially preferably 20 to 50%.

The liquid detergent composition according to the invention is preferably physically stable in that it shows less than 2% by volume phase separation when made at 25 ° C. and then stored for 21 days.

The liquid detergent composition according to the present invention is preferably 20
It is volume stable in that it exhibits a volume increase of less than 25%, preferably less than 10%, more preferably less than 5% when stored at a temperature of ~ 37 ° C for 3 months.

To obtain good volume stability, preferably according to the invention
The composition further comprises a second stabilizer for the bleaching component.
Mu. Suitable stabilizers are well known in the art and include EDTA, silicic acid.
Magnesium and phosphonates such as Dequest
(Monsanto) and naphthol (Merck)
Includes. Preferably, the amount of these stabilizers is in the composition
0.05 to 5% by weight, more preferably 0.
It is from 05 to 1%.

The compositions of the present invention may also include one or more bleach precursors. A well known example of this type of drug is TAED. Preferably the standard precursor is present in the system in at least partially undissolved form. One way to ensure that the precursor is present in undissolved form is to increase the amount of electrolyte in the composition to reduce the solubility of the precursor in the system. Suitable electrolytes for this purpose are, for example, at least partially water-soluble carbonates, sulphates and halides.

In use, the detergent composition of the present invention is diluted with wash water to make a wash liquor, for example for use in a washing machine. The concentration of the liquid detergent composition in the wash liquor is preferably
It is 0.05 to 10% by weight, more preferably 0.1 to 3% by weight.

To ensure effective detergent properties, the liquid detergent composition is preferably alkaline and has a pH in the range of about 7.0 to 12, preferably about 8 to about 11 when the composition is used in an aqueous solution at the recommended concentration. Is preferably given. To meet this requirement, the undiluted liquid composition should preferably have a pH greater than 7, such as about pH 8.0 to about 12.5. Excessively high p
H, eg a pH above about pH 13, is less desirable for home safety. When hydrogen peroxide is present in the liquid composition, the pH generally ensures a combined effect of good detergent properties and good physical and chemical stability.
7.5-10.5, preferably 8-10, especially 8.5-10. Of course, the components of this type of highly alkaline detergent composition should be selected for alkaline stability, especially for pH-sensitive substances such as enzymes (especially suitable proteolytic enzymes). The pH can be adjusted by adding suitable alkaline or acidic substances.

The composition according to the invention can be produced by any method for producing a liquid detergent composition. A preferred method involves the addition of alkali metal silicate to water, which may optionally include one or more of the other ingredients in the composition. The bleaching material is preferably added as a predispersion.

Hereinafter, the present invention will be further described with reference to examples. In all examples, all percentages are by weight unless otherwise stated.

EXAMPLES The following compositions were made by adding each component to water in the order given below: Composition A had a pH of about 11, contained about 1.9% by weight bleaching material in dissolved form, and had a bleach half-life at 37 ° C of 35 days. Composition B has a pH of about 9.8 and is about 2.1% by weight.
Of bleaching material in dissolved form. The half-life of dissolved bleach was significantly shorter than one day.

This example clearly shows that alkali metal disilicates can be used to advantage in stabilizing bleaching agents.

Example II The following liquid detergent compositions can be formulated by adding the ingredients in water in the order given below.

Example III Warming the electrolyte with minor components except perfume and enzyme
Water, then peptizing polymer, then wash.
The active ingredient is added as a premix under stirring and
After cooling the mixture and adding the enzyme and flavor,
The composition of was made:Perborate is a 65% predispersion in water (proxy
Le , ICI), and the polymer is A in EP 346995.
The deflocculating polymer described as 44, and the pH is
Adjusted with citric acid.

The viscosity of the product is measured at 21 s ^-1 in mPa · s, the volume stability is determined by measuring the maximum volume increase when stored at room temperature for 3 months, and the physical stability is determined by phase separation during storage. And determined by solids settling, bleach stability indicates% bleach remaining after 4 weeks storage at 37 ° C. The following results were obtained: These results indicate that good bleach stability is obtained when the alkali metal disilicate is used in combination with the bleach.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Olsorn, Theresia Maria The Netherlands, N. El. 3137. B. Behr. Fraderdingen, Robert Schümannling, 49 (56) References 2-189397 (JP, A)

Claims (5)

[Claims] 1. Water, 10-30% by weight of detergent active material, 1-40
A liquid detergent composition comprising, by weight, solid particulate peroxygen bleaching material, and 0.4-5% by weight alkali metal silicate material. 2. A liquid detergent composition according to claim 1 wherein the bleaching material is selected from the group consisting of perborate and percarbonate bleaches. 3. The liquid detergent composition according to claim 1, wherein the alkali metal silicate material is an alkali metal disilicate. 4. A liquid detergent composition according to claim 1 containing from 7 to 30% by weight of said bleaching agent. 5. A liquid detergent composition according to claim 1 containing 5 to 50% by weight of non-soap builder material.